CN106062249B - Zinc-based metal plated steel sheet and its manufacturing method - Google Patents

Zinc-based metal plated steel sheet and its manufacturing method Download PDF

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Publication number
CN106062249B
CN106062249B CN201580010893.0A CN201580010893A CN106062249B CN 106062249 B CN106062249 B CN 106062249B CN 201580010893 A CN201580010893 A CN 201580010893A CN 106062249 B CN106062249 B CN 106062249B
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zinc
steel sheet
based metal
coating
plated steel
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CN106062249A (en
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星野克弥
平章一郎
名越正泰
花田一利
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JFE Engineering Corp
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NKK Corp
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • C25D3/00—Electroplating: Baths therefor
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    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
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Abstract

The present invention provides a kind of manufacturing method of zinc-plated system's zinc-based metal plated steel sheet, resistance to sliding when the zinc-based metal plated steel sheet compression moulding is small, and also there is excellent degreasing under the conditions of the harsh alkali degreasing that temperature is low, production line length is short, be able to suppress the dissolution for being formed by oxide skin(coating) and inhibit the uneven generation caused by cleaning treatment.The manufacturing method of above-mentioned zinc-based metal plated steel sheet has following process: oxide skin(coating) formation process, is kept for 1~60 second after contacting zinc-based metal plated steel sheet with the acid solution containing sulfate ion, is followed by washed；And neutralisation treatment operation, holding 0.5 second or more in the state that the surface of the oxide skin(coating) formed in making above-mentioned oxide skin(coating) formation process and alkaline aqueous solution contact, it followed by washes, is dry, above-mentioned alkaline aqueous solution contains the carbanion of the P ion of 0.01g/L or more, 0.1g/L or more.

Description

Zinc-based metal plated steel sheet and its manufacturing method
Technical field
The present invention relates to the sliding property (slidability) in compression moulding and the alkali degreasings in the manufacturing process of automobile (alkali degreasability) excellent zinc-based metal plated steel sheet (galvanized steel sheet) and its manufacturing method. After, it also include alloy galvanized steel plate (galvannealed with " zinc-based metal plated steel sheet (galvanized steel sheet) " Steel sheet) form record.
Background technique
Zinc-based metal plated steel sheet is widely used centered on car body purposes in extensive field.It is this zinc-plated on the way Be steel plate be carried out compression moulding (press forming), coating (paint) and for using.
But zinc-based metal plated steel sheet has compression moulding (press compared with cold-rolled steel sheet (cold-rolled steel) Formability) poor disadvantage.This is because resistance to sliding (the sliding of the zinc-based metal plated steel sheet in compacting tool set Resistance) big compared with cold-rolled steel sheet.That is, the part big in the resistance to sliding of mold and press strip (bead), zinc-plated system's steel Plate difficultly flows into compacting tool set, easily causes the fracture of steel plate.
The highly viscous lubrication of coating is widely used in the method for compression moulding when as the use for improving zinc-based metal plated steel sheet The method of oil.But in this method, shortage of oil (oil shortage) when due to compression moulding, there are suppression performances to become The problems such as unstable.Therefore, it is strongly required to improve the compression moulding of zinc-based metal plated steel sheet itself.
However, in recent years, the simplification of production process, reduction of carrying capacity of environment substance in production process etc. are attempted.Especially It is the shortening for carrying out the production line length of alkali degreasing (alkali degreasing) process of the pre-treatment as coating process Change, the low temperature of operating environment in alkali degreasing process.It is required that even if under conditions of this harsh, it will not be to coating process Cause the dysgenic steel plate with excellent degreasing.
Therefore, as the zinc-based metal plated steel sheet of automobile, it is desirable that while there is excellent compression moulding, tighter than previous Also with the steel plate of excellent degreasing under the conditions of severe alkali degreasing.
As the method for improving compression moulding, it can enumerate and form lubrication envelope on the surface of zinc-based metal plated steel sheet The technology of (lubricant film) or the technology for forming oxide skin(coating) (oxide layer).
It is disclosed in patent document 1 through electrolysis processing, impregnation, coating oxidation processes or heat treatment in galvanized steel The Surface Creation Ni oxide of plate (zinc coated steel sheet), to make compression moulding and chemical conversion treatment Property (chemical conversion ability) improve technology.
It is disclosed in patent document 2,3 by making alloyed hot-dip galvanized steel plate (hot-dip galvannealed Steel sheet) it is contacted with sulfuric acid solution, the oxide skin(coating) based on Zn oxide is formed in surface of steel plate, is inhibited The adhesion of alloyed hot-dip zinc-coated layer (hot-dip galvannealed coating layer) and compacting tool set, make sliding property The technology of raising.
As the method for improving degreasing, the skill cleaned with the solution of alkalinity, the solution containing P (phosphorus) can be enumerated Art.
The surface by cleaning alloyed hot-dip galvanized steel plate with the solution of alkalinity is disclosed in patent document 4, makes degreasing Property improve technology.
It discloses in patent document 5 and is cleaned by the solution containing P with the surface of alloyed hot-dip galvanized steel plate, make degreasing Property improve technology.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 03-191093 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2002-256448 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2003-306781 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2007-016266 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2007-016267 bulletin
Summary of the invention
However, in Patent Documents 1 to 3, by lubricant for containing etc. or by the obtained lubricant effect of reaction layer, The lubricity between compacting tool set and zinc-based metal plated steel sheet is embodied, but for degreasing, is unable to satisfy and requires characteristic.Patent document 4 In~5, degreasing improvement is observed, but the situation that the effect may not be abundant is observed under harsh degreasing condition.
The present invention makes in view of the foregoing, and the purpose is to provide a kind of zinc-based metal plated steel sheet and zinc-based metal plated steel sheet Manufacturing method, the resistance to sliding when zinc-based metal plated steel sheet compression moulding is small, and that temperature is low, production line length is short is harsh Also there is excellent degreasing under the conditions of alkali degreasing, be able to suppress the dissolution for being formed by oxide skin(coating) and inhibit by cleaning treatment The generation of caused unevenness (unevenness).
The present inventor etc. further investigate in order to solve the above problems and repeatedly.Its result, which specifies, is formed in steel plate The oxide skin(coating) on surface use containing with P concentration being calculated as the P ion of 0.01g/L or more, be calculated as with carbon acid ion concentration The alkaline aqueous solution of the carbanion of 0.1g/L or more and after being neutralized, by the oxygen intensity conversion of measurement at conduct SiO2Value obtained by the thickness of envelope is 20nm or more (thickness for being equivalent to oxide skin(coating)), and contains 50mg/m2Above Zn, 5mg/m2Above S, the 0.2mg/m2C, 0.2mg/m2Above P, so that resistance to sliding when compression moulding is small, and degreasing Well, it is able to suppress the dissolution for being formed by oxide skin(coating) and inhibits the unevenness caused by cleaning treatment, discovery can solve State project.
The present invention is based on above-mentioned opinion, feature is as follows.
(1) a kind of zinc-based metal plated steel sheet (galvanized steel sheet), which is characterized in that have steel plate and be formed in Zinc-plated system layer (galvanized coating layer) on the steel plate, above-mentioned coating layer have average thickness 20nm on surface layer Above oxide skin(coating), above-mentioned oxide skin(coating) are made of Zn, O, H, S, C, P and inevitable impurity, contain 50mg/m2More than Zn, 5mg/m2Above S, the 0.2mg/m2Above C, the 0.2mg/m2Above P.
(2) zinc-based metal plated steel sheet as described in (1), which is characterized in that above-mentioned oxide skin(coating) there are sulfate, carbonyldioxy, Hydroxyl and phosphate.
(3) zinc-based metal plated steel sheet as described in (1) or (2), which is characterized in that include Zn in above-mentioned oxide skin(coating)4(SO4)1-X (CO3)X(OH)6·nH2The crystal structure object that O is indicated.Here, X is the real number of 0 < X < 1, and n is the real number of 0≤n≤10.
(4) zinc-based metal plated steel sheet as described in any one of (1)~(3), which is characterized in that contain in above-mentioned oxide skin(coating) Selected from PO4 3-、P2O7 4-、P3O9 5-One or more of with these inorganic acids or metallic compound, above-mentioned metallic compound, which contains, to be selected from One or more of sodium and zinc.
(5) zinc-based metal plated steel sheet as described in any one of (1)~(4), which is characterized in that zinc-based metal plated steel sheet is alloying heat Dip galvanizing steel sheet (hot-dip galvannealed steel sheet), hot-dip galvanized steel sheet (hot-dip galvanized Steel sheet) or plated steel sheet (electrogalvanized steel sheet).
(6) a kind of manufacturing method of zinc-based metal plated steel sheet is the manufacture of zinc-based metal plated steel sheet described in any one of (1)~(5) Method, which is characterized in that have following process: oxide skin(coating) formation process makes zinc-based metal plated steel sheet and containing sulfate ion It is kept for 1~60 second after acid solution contact, is followed by washed；And neutralisation treatment operation, form above-mentioned oxide skin(coating) The surface of the oxide skin(coating) formed in process is kept 0.5 second or more in the state of contacting with alkaline aqueous solution, followed by wash, Dry, above-mentioned alkaline aqueous solution, which contains, to be calculated as the P ion of 0.01g/L or more with P concentration, is calculated as with carbon acid ion concentration The carbanion of 0.1g/L or more.
(7) manufacturing method of the zinc-based metal plated steel sheet as described in (6), which is characterized in that above-mentioned alkaline aqueous solution, which contains, to be selected from The phosphorus compound and carbonate of one or more of phosphate, pyrophosphate and triphosphate.
(8) manufacturing method of the zinc-based metal plated steel sheet as described in (6) or (7), which is characterized in that containing dense with carbanion Degree is calculated as the above-mentioned carbanion of 0.6g/L or more.
(9) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(8), which is characterized in that containing with carbonic acid Ion concentration is calculated as the above-mentioned carbanion of 1.2g/L or more.
(10) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(9), which is characterized in that above-mentioned alkalinity The pH of aqueous solution is 9~12, and temperature is 20~70 DEG C.
(11) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(10), which is characterized in that above-mentioned acidity Solution has pH buffer function, and the range that pH rising degree is 0.003~0.5, above-mentioned pH rising degree is the above-mentioned acidity by making 1L The pH of solution from 2.0 rise to 5.0 needed for the amount (L) of 1.0mol/L sodium hydroxide solution define.
(12) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(11), which is characterized in that above-mentioned acidity Solution contain total 5~50g/L selected from acetate, phthalate, citrate, succinate, lactate, tartaric acid The salt of one or more of salt, borate and phosphate, pH are 0.5~5.0, and liquid temperature is 20~70 DEG C.
(13) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(12), which is characterized in that above-mentioned oxidation In nitride layer formation process, the above-mentioned acid solution adhesion amount of the surface of steel plate after above-mentioned acid solution contact is 15g/m2Below.
(14) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(13), which is characterized in that above-mentioned zinc-plated Be steel plate be alloyed hot-dip galvanized steel plate, hot-dip galvanized steel sheet or plated steel sheet.
(15) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(14), which is characterized in that steel plate After implementing zinc-plated system, before above-mentioned oxide skin(coating) formation process, by making steel plate and the aqueous solution of alkalinity make surface and contact Activation.
(16) manufacturing method of the zinc-based metal plated steel sheet as described in any one of (6)~(15), which is characterized in that steel plate After implementing zinc-plated system, before above-mentioned oxide skin(coating) formation process, implement skin-pass (temper rolling).
According to the present invention, it can be obtained zinc-based metal plated steel sheet, resistance to sliding when compression moulding is small and low, raw in temperature Also there is excellent degreasing under the conditions of the short harsh alkali degreasing of producing line length, be able to suppress and be formed by the molten of oxide skin(coating) Solution and the generation for inhibiting the unevenness caused by cleaning treatment.
Detailed description of the invention
Fig. 1 is the brief main view for indicating measuring friction coefficient device.
Fig. 2 is the brief perspective views for indicating the geomery of the press strip used under the condition 1 of embodiment.
Fig. 3 is the brief perspective views for indicating the geomery of the press strip used under the condition 2 of embodiment.
Fig. 4 is the brief perspective views for indicating the geomery of the press strip used under the condition 3 of embodiment.
Fig. 5 is the schematic diagram for indicating the evaluation criteria for evaluating appearance unevenness.
Specific embodiment
Hereinafter, embodiments of the present invention will be described.
The manufacturing method of zinc-based metal plated steel sheet of the invention is characterized in that having following process: oxide skin(coating) formation process, It is kept for 1~60 second after contacting zinc-based metal plated steel sheet with the acid solution (sulfuric acid solution) containing sulfate ion, it is laggard Row washing；And neutralisation treatment operation, the surface of the oxide skin(coating) formed in making oxide skin(coating) formation process and alkalinity are water-soluble It is kept in the state of liquid contact 0.5~10 second, followed by washes, is dry, above-mentioned alkaline aqueous solution contains to be calculated as with P concentration The P ion of 0.01g/L or more, the carbanion that 0.1g/L or more is calculated as with carbon acid ion concentration.Hereinafter, to each process into Row explanation.
Firstly, implementing before oxide skin(coating) formation process zinc-plated.Implement zinc-plated method to be not particularly limited, can be used The general methods such as galvanizing by dipping (hot-dip galvanizing), electrogalvanizing (electrogalvanizing).In addition, electric Zinc-plated, galvanizing by dipping treatment conditions are not particularly limited, using appropriate optimum condition.It should be noted that carrying out hot-dip When zinc processing, Al is preferably added in plating bath from slag countermeasure aspect.In this case, in plating bath except Al with Outer addition element ingredient is not particularly limited.That is, in addition to Al, contain or add Pb, Sb, Si, Sn, Mg, Mn, Ni, Ti, Li, Cu etc. will not damage effect of the invention.
In turn, after implementing galvanizing by dipping, Alloying Treatment (galvannealing) also can be implemented.In the present invention, close The condition of aurification processing is not particularly limited, using appropriate optimum condition.
As steel plate, the steel plate that implements the steel plate of zinc-plated system's processing, implement after the processing of zinc-plated system Alloying Treatment It can be used.Here, the steel grade of steel plate is not particularly limited, and mild steel (low-carbon steel), ultra-low carbon steel can be used The various steel plates such as (ultralow-carbon steel), IF steel, the high-tensile steel for being added to various alloying elements.In addition, making For base material steel plate, hot rolled steel plate, cold-rolled steel sheet can be used to can be used.
Steel plate used in the present invention is the steel plate for implementing the rear Alloying Treatment of zinc-plated system's processing, that is, alloying heat In the case where dip galvanizing steel sheet, the flat part (top surface (top face) of concave-convex protrusion) on the surface of alloyed hot-dip zinc-coated layer The area ratio be preferably set to 20~80%.When less than 20%, with the compacting tool set of the part (recess portion) other than flat part Contact area becomes larger, and the thickness of aftermentioned oxide skin(coating) can be reliably controlled in the area actually contacted with compacting tool set The area ratio of flat part becomes smaller.As a result, the improvement of compression moulding becomes smaller.In addition, the part other than flat part Have the function of keeping punching oil in compression moulding.Therefore, if the area ratio of flat part is greater than 80%, in alloyed hot-dip Shortage of oil is easily caused when the compression moulding of galvanized steel plain sheet, the improvement of compression moulding becomes smaller.
It should be noted that the flat part of alloyed hot-dip zinc-coated layer surface can be by with optical microscopy or scanning electron Microscope etc. is observed surface and is readily recognized.The area ratio in the flat part of alloyed hot-dip zinc-coated layer surface can be by right Above-mentioned microscope photo carries out image analysis and finds out.
In addition, preferably after implementing zinc-plated system, before oxide skin(coating) formation process, implementing skin-pass in the present invention. By implementing skin-pass, the bumps on surface are mitigated due to planarization.As a result, mold crushes plating in compression moulding The decline of power needed for the protrusion on surface, can be such that sliding properties improve.
Especially since the reactive difference at the interface of steel plate and plating when the Alloying Treatment, in alloyed hot-dip Galvanized steel sheet surface exists concave-convex.In order to significantly improve with the manufacturing method of the present invention manufacture alloyed hot-dip galvanized steel plate with Sliding property between compacting tool set, it is important that skin-pass is implemented to steel plate.
In turn, in the present invention, preferably after implementing zinc-plated system, before oxide skin(coating) formation process, by with alkalinity Aqueous solution contacts and makes surface active.The especially previous thickness of hot-dip galvanized steel sheet, plated steel sheet with most surface layer is small In the oxide skin(coating) (unwanted oxide skin(coating)) of 10nm, Zn or Al as impurity element etc..By water-soluble using alkalinity Liquid removes the unwanted oxide skin(coating), oxide skin(coating) can be promoted to be formed instead in next oxide skin(coating) formation process It answers, can be manufactured with the shorter time.Alkaline aqueous solution used in the activation processing is preferably the range of pH10~14.pH When less than 10, unwanted oxide skin(coating) can not be completely removed sometimes.If pH is greater than 14, become the dissolution of zinc-plated system's layer sometimes By force, surface stain, burn the state of (burnt deposit).In addition, aqueous solution alkaline used in the activation processing is preferred The range that temperature is 20 DEG C~70 DEG C.If the dereaction of removing of unwanted oxide skin(coating) needs for a long time sometimes less than 20 DEG C, It is likely to result in the decline of productivity.On the other hand, when being greater than 70 DEG C, although reaction carries out quickly, hold in surface of steel plate It is also easy to produce and burns, handles unevenness.The type of solution does not limit, it is preferable to use the reagents such as NaOH from the viewpoint of cost.This Outside, substance, other ingredients in addition to may include the element contained by the zinc-plated system such as Zn, Al, Fe in alkaline aqueous solution.
Then, making zinc-based metal plated steel sheet, (sulfuric acid exists in the state of sulfate ion with the acid solution containing sulfuric acid In acid solution.In addition, following be labeled as " sulfuric acid solution " sometimes.) 1~60 second, followed by water are kept after contact It washes, forms oxide skin(coating) on the surface of steel plate.Hereinafter, being illustrated to the oxide skin(coating) formation process.
The mechanism for forming oxide skin(coating) in oxide skin(coating) formation process is still not clear, but is contemplated that as follows.If thinking to make Steel plate is contacted with sulfuric acid solution, then the dissolution of zinc occurs by steel plate side.Hydrogen occurs simultaneously and generates reaction for the dissolution of the zinc, because If this carries out the dissolution of zinc, the hydrogen ion concentration in solution is reduced, as a result, the pH of solution rises, in above-mentioned surface of steel plate Form the oxide skin(coating) based on Zn.
As long as sulfuric acid solution used in oxide skin(coating) formation process dissolves zinc and can form oxide skin(coating) The pH of degree is not particularly limited (detailed content is told about later).The adjusting of pH uses sulfuric acid.By using sulfuric acid, sulfuric acid acid Property solution become the acid solution comprising sulfate ion.Sulfate ion concentration in sulfuric acid solution is preferably 0.5~ 50g/L.If sulfate ion concentration is less than 0.5g/L, the quantitative change of the sulfate in oxide is few, and the S amount in oxide skin(coating) is small In 5mg/m2, it is difficult to form Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure object that O is indicated.If sulfate ion concentration is big Exist in 100g/L, although then will lead to cost increase without the problem in quality, therefore not preferably.
In the present invention, it is preferable to use also with the sulfuric acid solution of pH buffer function in sulfuric acid solution.Have The sulfuric acid solution of pH buffer function is compared with the sulfuric acid solution for not having pH buffer function, it is difficult to make the pH wink of solution Between rise, the oxide skin(coating) of sufficient amount easy to form.In addition, if the sulfuric acid solution used has pH buffer function, it can It is enough stably formed the oxide skin(coating) of excellent in sliding property, therefore metal ion, inorganic compound etc. can be contained in the solution.
The pH buffer function of sulfuric acid solution can be evaluated by pH rising degree, which is by making 1 liter Acid solution pH rise to 2.0~5.0 needed for the amount (L) of 1.0mol/L sodium hydrate aqueous solution define.The present invention In, range of the value 0.003~0.5.Quickly cause on pH if pH rising degree less than 0.003, is unable to get sometimes It rises and is enough to form the dissolution of the zinc of oxide skin(coating), without the formation of the oxide skin(coating) of sufficient amount.On the other hand, it is believed that if PH rising degree is greater than 0.5, then excessively promotes the dissolution of zinc sometimes, the formation of oxide skin(coating) sometimes needs for a long time, or plates sometimes The damage of coating becomes acutely, and also loses the effect as Rustproof Steel Plate originally sometimes.Here, pH is greater than 2.0 acidity The pH rising degree of solution is that the range by sulfuric acid etc. in pH=2.0~5.0 makes an addition to sulfuric acid almost without the inorganic acid of resiliency Acid solution and so that pH is temporarily dropped to 2.0 and is evaluated.
As this acid solution with pH buffer function, can enumerate comprising sodium acetate (CH3) etc. COONa acetates, Potassium Hydrogen Phthalate ((KOOC) C6H4(COOH)) phthalates, sodium citrate (Na such as3C6H5O7) or dihydrogen citrate Potassium (KH2C6H5O7) etc. citrates, sodium succinate (Na2C4H4O4) etc. succinates, sodium lactate (CH3CHOHCO2The lactic acid such as Na) Salt, sodium tartrate (Na2C4H4O6) etc. tartrates, borate, phosphate etc. acid solution.It is preferred that total with 5~50g/L Range contain selected from they one or more of salt.If being less than 5g/L, with the dissolution of zinc, the pH of solution rise compared with It generates fastly, therefore the oxide skin(coating) for being enough to improve sliding property can not be formed sometimes.If more than 50g/L, then promote the dissolution of zinc, Not only the formation of oxide skin(coating) needs long time, but also the damage of coating layer sometimes is also violent, loses and is used as antirust originally The effect of steel plate.
In addition, the preferred pH of sulfuric acid solution is 0.5~5.0.When pH is less than 0.5, the dissolution of zinc is promoted, but is difficult to give birth to At oxide skin(coating).On the other hand, when pH is greater than 5.0, the reaction speed of zinc dissolution is lower.
In addition, the liquid temperature of sulfuric acid solution is preferably 20~70 DEG C.If less than 20 DEG C, the generation of oxide skin(coating) sometimes Reaction needs for a long time, it is possible to lead to the decline of productivity.On the other hand, when being greater than 70 DEG C, reaction carries out quickly, but anti- And it is uneven to be easy to produce processing in surface of steel plate.
The method for contacting above-mentioned steel plate with above-mentioned sulfuric acid solution is not particularly limited, and has and is impregnated in above-mentioned steel plate The method of sulfuric acid solution, the method that sulfuric acid solution is sprayed to above-mentioned steel plate, via applicator roll by sulfuric acid solution The method etc. for being coated on above-mentioned steel plate.In the present invention, the sulfuric acid solution film of thin shaped liquid film is preferably finally made to be present in steel Plate surface.This is because, it is assumed that it is more in the amount of the sulfuric acid solution of surface of steel plate if it exists, it is likely that even if zinc occurs Dissolution, the pH of solution are also difficult to rise, when the dissolution of zinc persistently occurs, and spending very long sometimes until forming oxide skin(coating) Between.In addition, more in the amount of the sulfuric acid solution of surface of steel plate if it exists, then the damage of alloyed hot-dip zinc-coated layer is also acute sometimes It is strong, the effect originally as Rustproof Steel Plate can be also lost sometimes.From this viewpoint, the steel plate table after sulfuric acid solution contact The sulfuric acid solution adhesion amount in face is preferably 15g/m2Below.In addition, from the viewpoint of the drying for preventing liquid film preferably 1g/m2More than.The progress such as the adjustment of adhesion amount can use compression roller, air scrapes.The adhesion amount of sulfuric acid solution can Infrared moisture meter (the CHINO CORPORATION infrared moisture manufactured using CHINO Co., Ltd. Gauge it) is measured.
It is kept for 1~60 second after contacting zinc-based metal plated steel sheet with sulfuric acid solution.That is, after being contacted with acid solution extremely Time (to the retention time of washing) until washing needs to be 1~60 second.If being utilized to the time washed less than 1 second The pH of solution rises to form the oxide skin(coating) based on Zn before sulfuric acid solution be washed off, therefore cannot get sliding property Improvement effect.Even if being greater than 60 seconds, the amount of oxide skin(coating) also can't see variation.In addition, for above-mentioned holding, from promotion oxidation Aspect is set out, and is preferably carried out under the atmosphere comprising the oxygen more than atmosphere.
In finally being washed for oxide skin(coating) formation process.Method, the condition of washing are not particularly limited.Not into It goes in the case where washing, the neutralisation treatment that the salt with pH buffer function being occasionally present in acidic treatment liquid continues behind It hinders to react with the alkaline aqueous solution of the pH9-12 containing carbanion in process.It is especially possible to not to be mixed into enough Carbanion, and cause degreasing, a part sliding properties decline.It is therefore preferable that carrying out 1 second or more sufficient Washing.
From the viewpoint of preventing the adhesion with compacting tool set and improving sliding property, preferably in compression moulding and pressing die The part of tool contact is made of hard and dystectic substance.The oxide skin(coating) formed in oxide skin(coating) formation process be hard and High-melting-point.Therefore, the adhesion with compacting tool set can be prevented, it is effective to the raising of sliding properties.If especially implementing tune Implement the processing for being formed uniformly oxide skin(coating) on the surface flat part of the above-mentioned steel plate of matter rolling, then can stably obtain good Good sliding property.
In addition, by the contact with compacting tool set, oxide skin(coating) wears and is eliminated, therefore aoxidizes in compression moulding The thickness of nitride layer needs not damage the degree of effect of the invention.Required thickness is according to the journey processed using compression moulding Degree and it is different.For example, with the big processing of the contact area of the processing of big deformation, compacting tool set and oxide skin(coating) the case where Under, it is desirable that thicker oxide skin(coating).For example, the thickness of the range adjustment oxide skin(coating) in 20~200nm.By that will aoxidize The average thickness of nitride layer is set as 20nm or more, can obtain the zinc-based metal plated steel sheet for showing good sliding property.If by oxide skin(coating) It is then more effective that thickness is set as 25nm or more.This is because in the contact area of compacting tool set and machined object (zinc-based metal plated steel sheet) In the compression moulding processing to become larger, though in the case where the abrasion of the oxide skin(coating) on surface layer, also can residual oxidization nitride layer, and almost The decline of sliding property is not will lead to.On the other hand, the upper limit of the thickness of oxide skin(coating) is not particularly limited.But if oxide The thickness of layer is greater than 200nm, then the reactivity on surface declines to heavens sometimes, it is difficult to form chemical conversion treatment envelope.Therefore, The thickness of oxide skin(coating) is preferably set to 200nm or less.The adjustment of specific thickness is by suitably changing to form following oxide skin(coating)s When condition and carry out.
Then, what the surface of the oxide skin(coating) formed in making above-mentioned oxide skin(coating) formation process was contacted with alkaline aqueous solution It is kept under state 0.5 second or more, followed by washes, is dry, being neutralized.Hereinafter, being carried out to the neutralisation treatment operation Explanation.
Alkaline aqueous solution, which contains, to be calculated as the P ion of 0.01g/L or more with P concentration, is calculated as 0.1g/ with carbon acid ion concentration The carbanion of L or more.It is contacted by making the alkaline aqueous solution containing P ion and carbanion with oxide skin(coating), in temperature Spend it is low, because produce line length it is short due to short processing time harsh alkali degreasing under the conditions of can also embody excellent degreasing.This In, temperature is low to refer to such as 35~40 DEG C, and production line length is short and short processing time refers to 60~90 seconds.
Improve mechanism to the degreasing to be still not clear, but is believed that as follows.If sulfuric acid solution remains on washing, drying Oxide layer surface afterwards, then the etch quantity on surface increases, and generates small bumps, becomes strong with the compatibility of oil.By with alkali It property aqueous cleaning and fully neutralizes, can prevent sulfuric acid solution from remaining on surface.In turn, if alkaline aqueous solution contains P Ion is then being formed by oxide layer surface attachment P ion.Think that P ion for synthetic detergent etc., has cleaning action, Even if therefore also contributing to degreasing under the conditions of harsh alkali degreasing.Here, carbanion if it exists, then in oxide skin(coating) It has inside been mixed into carbanion, has changed crystal structure.Meanwhile physical property also changes, and declines with the affinity of oil, degreasing improves. In turn, the dissolution reaction decline using the oxide skin(coating) of P ion is caused because of the variation of physical property, therefore is formed by oxide skin(coating) Meltage be remarkably decreased.At the same time, reacting by up to the present P ion and oxide skin(coating), is able to solve due to oxygen The problems such as appearance unevenness, the stability of compression moulding that compound layer thickness generates difference and generates decline.
From the viewpoint of obtaining the effect caused by using above-mentioned alkaline aqueous solution, that is, in order in oxide layer surface Adhere to P ion and facilitate degreasing, the concentration of P ion contained by alkaline aqueous solution is set as 0.01g/L or more in terms of P.In terms of P Preferably 0.1g/L~20g/L.P will not fully be attached to oxide skin(coating) sometimes if being less than 0.01g/L.If more than 20g/L It is then possible to dissolution and is formed by oxide skin(coating).
The type that the phosphorus compound of P ion is supplied in alkaline aqueous solution is not particularly limited, from the viewpoint of cost and supply It sets out and is preferably selected from one or more of phosphate, pyrophosphate, triphosphate.
From the viewpoint of obtaining the effect caused by using above-mentioned carbanion, that is, affine with oil in order to reduce Power and further increase degreasing, and in order to reduce the dissolution of oxide skin(coating) reaction, prevent that appearance is uneven, realizes compression moulding Stabilisation, the concentration of the carbanion in alkaline aqueous solution is set as 0.1g/L or more in terms of carbanion.If being less than 0.1g/L, then carbanion being mixed into the oxide layer becomes inadequate, and is unable to fully change physical property.Preferably 0.6g/L ~500g/L.If considering the variation of concentration when production, more preferably 1.2g/L or more.On the other hand, from production cost Viewpoint is set out preferably 100g/L or less.
In addition, carbanion is not particularly limited.It can be blown into carbon dioxide, or use sodium carbonate, manganese carbonate, carbonic acid Nickel, potassium carbonate and its hydrate.The use of foregoing illustrative carbon dioxide and carbonate is from the viewpoint of cost and supply And it is preferred.
As long as the pH of above-mentioned alkaline aqueous solution is alkalinity, there is no particular limitation, pH is preferably 9~12.If pH be 9 with On, then it can be sufficiently carried out neutralisation treatment.In addition, if pH be 12 hereinafter, if be easy to prevent the dissolution of Zn layers of plating.
The liquid temperature of above-mentioned alkaline aqueous solution is not particularly limited, and preferably 20~70 DEG C.If liquid temperature is 20 DEG C or more, instead Speed is answered to increase.If liquid temperature be 70 DEG C hereinafter, if oxide film thereon dissolution be suppressed.
The method for contacting alkaline aqueous solution with oxide skin(coating) is not particularly limited, and is impregnated in alkaline aqueous solution and is connect The method of touching, by alkaline aqueous solution carry out it is spraying and contact method, using applicator roll alkaline on the oxide layer The method etc. of aqueous solution.
The time for contacting alkaline aqueous solution with oxide skin(coating) is set as 0.5 second or more.By being set as 0.5 second or more, Excellent degreasing can be assigned to zinc-based metal plated steel sheet.
Next, being illustrated to the composition of zinc-based metal plated steel sheet of the invention.
Oxide skin(coating) is made of Zn, O, H, S, C, P and inevitable impurity, contains 50mg/m2Above Zn, the 5mg/m2 Above S, the 0.2mg/m2Above C, the 0.2mg/m2Above P.
Then from the viewpoint of sliding property, Zn content is 50mg/m2It is above 5mg/m with S content2It is necessary above.This Outside, from the viewpoint of weldability, chemical convertibility, preferably Zn content is 1000mg/m2Hereinafter, and S content be 100mg/m2Below.In addition, in order to which Zn content and S content are set as above range, using following manufacturing condition: making galvanized steel Plate is kept for 1~60 second after contacting with sulfuric acid treatment fluid, is followed by washed.
From the viewpoint of degreasing, needing P content is 0.2mg/m2More than.In addition, from weldability, chemical conversion treatment From the perspective of property, P content is preferably 40mg/m2Below.From degreasing, the viewpoint of uneven, compression moulding the stability of appearance It sets out, needing C content is 0.2mg/m2More than.In addition, C content is preferred from the viewpoint of weldability, chemical convertibility For 40mg/m2Below.In addition, in order to which P content and C content are set as above range, using making it and contain P ion and carbonate The manufacturing condition of the alkaline aqueous solution contact of ion.
In addition, oxide skin(coating) contains H.Analysis is quantitatively carried out to H to be difficult.By using x-ray photoelectron spectroscopy Instrument (X-ray photoelectron spectrometer) analyzes the existing forms of Zn, and the presence of H can be confirmed.Zn With Zn (OH)2Form in the presence of, if using Al Ka monochromatic radiation source, implement be equivalent to Zn LMM spectrum narrow scan survey Fixed (narrow scan measurement), then observe peak near 987eV.Thus, it is possible to determine presence and the OH base of H Presence.There is no special provision to the amount of H.Think that H exists substantially in the form of OH, thus H amount with the increase of oxygen amount and Increase.
In addition, from the viewpoint of by membrane stability, preferably in the oxide layer, there are sulfate, carbonyldioxy, hydroxyl and Phosphate.In addition, being kept for 1~60 second according to after contacting galvanized steel plain sheet with sulfuric acid treatment fluid, followed by wash, The manufacturing condition for contacting it with the alkaline aqueous solution containing carbanion, then make in oxide skin(coating) that there are sulfates, carbonic acid Base and hydroxyl.
Furthermore it is preferred that containing Zn in oxide skin(coating)4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure object that O is indicated.This In, X is the real number of 0 < X < 1, and n is the real number of 0≤n≤10.By the inclusion of above-mentioned crystal structure object, can be obtained by layered crystal Sliding deformation caused by sliding properties raising effect.This especially contributes to the raising of the sliding deformability at initial stage, In terms of influence it is big.In addition, the content of above-mentioned crystal structure object is excellent from the viewpoint of obtaining said effect It is selected as certifiable degree in aftermentioned embodiment.It should be noted that according to galvanized steel plain sheet is connect with sulfuric acid treatment fluid It is kept for 1~60 second, is followed by washed after touch, it is made to contact such manufacture item with the alkaline aqueous solution containing carbanion Part can then make oxide skin(coating) contain Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure object that O is indicated.
From the viewpoint of degreasing, preferred oxides layer contains selected from PO4 3-、P2O7 4-、P3O9 5-, their inorganic acid (PO4 3-、P2O7 4-、P3O9 5-Inorganic acid) and their metallic compound (PO4 3-、P2O7 4-、P3O9 5-Metallic compound) One or more of.Here, metallic compound refers to containing selected from PO4 3-、P2O7 4-And P3O9 5-One or more of and selected from hydrogen, The metallic compound of one or more of sodium and zinc.In addition, the content of the ingredient is preferred from the viewpoint of obtaining said effect For certifiable degree in aftermentioned embodiment.It should be noted that according to galvanized steel plain sheet is contacted with sulfuric acid treatment fluid It is kept for 1~60 second, is followed by washed afterwards, so that it is contacted such manufacturing condition with the alkaline aqueous solution containing P ion, then may be used So that oxide skin(coating) contains selected from PO4 3-、P2O7 4-、P3O9 5-, one or more of their metallic compound.
In addition, the metal oxide and/or hydroxide, other ingredients in addition to Zn can be contained in oxide skin(coating).By Comprising impurity etc. in sulfuric acid solution, S, N, P, B, Cl, Na, Mn, Ca, Mg, Ba, Sr, Si etc. are mixed into oxide skin(coating) sometimes In, it can contain however, as long as in the range that does not impair the effects of the present invention.
It should be noted that for oxide skin(coating), it is believed that generate oxide when being formed according to above-mentioned mechanism, therefore mark For " oxide skin(coating) ", in the present invention, the oxide amount as long as the specific range of the satisfactions such as thickness, Zn content, in oxide skin(coating) It is not particularly limited.
The oxide skin(coating) formed in the present invention can be analyzed by following methods.
For the thickness of oxide skin(coating), x-ray fluorescence analysis (fluorescent X-ray analysis) can be used It is measured, on the basis of the value of the silicon wafer of silica envelope of the resulting oxygen intensity to form known thickness, is converted into two Silica film thickness is simultaneously measured.
For Zn, S, P contained by oxide skin(coating) or other metal ions, ICP emission spectrum device can be used to utilization Solution made of 14% solution (% means quality %) of ammonium dichromate 2%+ ammonium hydroxide dissolution oxide skin(coating) is analyzed and is quantified. For C contained by oxide skin(coating), oxide skin(coating) is used into the stainless steel brush and ethyl alcohol of diameter 0.2mm or less, length 40mm or more Gas phase can be used so as to extract in the form of powdered ingredients by film component in scratch-off surface, the resulting ethanol solution of suction strainer Chromatographic mass spectrometry instrument carries out heating analysis to it and quantifies.
For the existing forms of C, can be used gaschromatographic mass spectrometric analysis to the oxide skin(coating) ingredient of similarly powdered into Row analysis.
For the crystallization water, differential thermal balance (differential thermogravimetric analyzer) point can be used The oxide skin(coating) ingredient of similarly powdered is analysed, 100 DEG C of weight reductions below are equivalent to the crystallization water.It should be noted that the crystallization water Refer to and is mixed into brilliant intracorporal hydrone.
S, the existing forms of Zn or O can be used x-ray photoelectron spectroscopy and be analyzed.It, can for the existing forms of P To be analyzed with X-ray absorption fine structure spectrometer.
It in turn, can be according to the diffraction maximum of the oxide skin(coating) obtained by X-ray diffraction by crystal structure for crystal structure It is specific.
Embodiment 1
Hereinafter, illustrating the present invention by embodiment.It should be noted that the present invention is not limited to following embodiments.
Galvanizing by dipping processing and Alloying Treatment are implemented to the cold-rolled steel sheet of plate thickness 0.7mm, then, carry out skin-pass. Next, handling as oxide skin(coating) formation, it is being adjusted to condition shown in table 1 (merge table 1-1 and table 1-2 and as table 1) Sulfuric acid solution in impregnate steel plate, after being squeezed with roller, keep table 1 shown in the stipulated time.Then, after being washed, It is dried.Next, being neutralized under the conditions shown in Table 1.
Here, the sulfate ion concentration of No.2~12, No.23~49, No.57~62 of table 1 is 15g/L.No.13~ 22,52~56 sulfate ion concentration is also 0.5~30g/L.
To the thickness of the oxide skin(coating) by alloyed hot-dip galvanized steel plate obtained above measurement surface, compression moulding is evaluated Property (sliding properties), degreasing and appearance it is uneven.Evaluation method described below.
(1) analysis of oxide skin(coating)
The Thickness Analysis of oxide skin(coating)
The measurement of the thickness of oxide skin(coating) uses fluorescent x-ray analyzer.The electricity of pipe ball (tube bulb) when measurement Pressure and electric current are set as 30kV and 100mA, and analyzing crystal (dispersive crystal) is set as TAP and detects O-K alpha ray. When measuring O-K alpha ray, the intensity in background positions is also measured in addition to its peak position, can calculate the Alpha-ray net intensity of O-K. It should be noted that the time of integration in peak position and background positions is respectively 20 seconds.
In addition, by the silicon wafer for the silica envelope for being formed with film thickness 96nm, 54nm and 24nm for being split into size appropriate It is set to sample table together with these a series of samples, the Alpha-ray intensity of O-K can also be calculated by these silica envelopes.Make It is made the calibration curve of oxide layer thicknesses Yu O-K alpha ray intensity with these data, calculates the thickness of the oxide skin(coating) of material to be tested Degree is as the oxide layer thicknesses to be converted with silica envelope.
The composition analysis of oxide skin(coating)
Oxide skin(coating) is only dissolved using 14% solution (% means quality %) of ammonium dichromate 2%+ ammonium hydroxide, is sent out using ICP Penetrate the quantitative analysis that spectral device (ICP emission spectrometry) implements Zn, S, P to the solution.
Oxide skin(coating) is resulting using diameter 0.15mm, the stainless steel brush of length 45mm and ethyl alcohol scratch-off surface, suction strainer Ethanol solution, thus by being extracted in the form of powdered ingredients by film component.Gas is used by film component by what is extracted as powder Phase chromatographic mass spectrometry instrument (gas chromatograph mass spectrometer) carries out heating analysis, to implement quantifying for C Analysis.Thermal decomposition furnace is connected in the leading portion of gas chromatography mass spectrometer.Extracted powdered sample is inserted into thermal decomposition furnace about 2mg makes the temperature of thermal decomposition furnace be warming up to 500 DEG C from 30 DEG C with 5 DEG C/min of heating rate, will be produced in thermal decomposition furnace with helium Raw gas is delivered in gas chromatography mass spectrometer, is analyzed gas composition.Column temperature when GC/MS is measured is set as 300 ℃。
The existing forms of C
Using gaschromatographic mass spectrometric analysis meter to similarly powdered being analyzed by film component for extracting, C is deposited Implement to analyze in form.
The existing forms of Zn, S, O, H
It is analyzed using existing forms of the x-ray photoelectron spectroscopy to S, Zn, O.Using Al Ka monochromatic radiation source, Implement the narrow scan measurement for being equivalent to the spectrum of Zn LMM, S 2p.
The existing forms of P
It is analyzed using existing forms of the X-ray absorption fine structure spectrometer to P.With high energy acclerator research institution The Beamline of (High Energy Accelerator Research Organization) Photon Factory BL27A implements the measurement of XAFS (X-ray absorption end fine structure *) at room temperature.It is monochromatic to the specimen surface irradiation of degreasing The radiating light of change, by absorbing current measurement (sample absorption current measurement) using sample All-electronin yield method (TEY) (total electron yield method) measures absorption edge XANES (the X-ray suction of P-K shell Structure * * near receiving end) spectrum.
*X-ray Absorption Fine Structure
The * X-ray Absorption Near-Edge Structure crystallization water quantifies
It is below using 100 DEG C of differential thermal balance (differential thermogravimetric analyzer) measurement Weight reduction amount.Powdered sample about 15mg is used in measurement.After sample is directed into device, with 10 DEG C/min of heating rate from Room temperature (about 25 DEG C) is warming up to 1000 DEG C, thermogravimetric amount variation when record heats up.
Crystal structure it is specific
The X-ray diffraction by film component implementing similarly powdered and extracting estimates crystal structure.Target uses Cu, Acceleration voltage 40kV, tube current (tube current) 50mA, scanning speed 4deg/min, under conditions of 2~90 ° of scanning range Implement measurement.
(2) evaluation method of compression moulding (sliding properties)
In order to evaluate compression moulding, the coefficient of friction of each material to be tested is measured in the following manner.
(i) dynamic friction coefficient measurement test: imagination squeezes inflow part
Fig. 1 is the brief main view for indicating measuring friction coefficient device.As shown in the drawing, the friction extracted from material to be tested Coefficient determination sample 1 is fixed in sample table 2, and sample table 2 is fixed on the upper surface of horizontally movable sliding stand 3.In cunning The lower surface of dynamic platform 3 is provided with the 5, the 1st load cell 7 of the sliding stand supporting table peace that can be moved up and down with the roller 4 being in contact with it Loaded on sliding stand supporting table 5, the 1st load cell 7 and pressing sliding stand supporting table 5 for being measured by press strip 6 The pressing load N to measuring friction coefficient sample 1 generated.2nd load cell 8 is installed on the one end of sliding stand 3, this 2 load cells 8 are used to measure the sliding for making sliding stand 3 mobile to horizontal direction in the state of acting on above-mentioned pressing force Resistance F.It should be noted that by the extruding of SUGIMURA Chemical Industrial Co. Ltd. system cleaning oil PRETON R352L(Sugimura Chemical Industrial Co.,Ltd.Wash Oil for Press Forming PRETON R352L) surface for being coated on sample 1 as lubricating oil is tested.
Fig. 2, Fig. 3 are the brief perspective views for indicating the geomery of used press strip.It is pressed in the lower surface of press strip 6 It is slided in the state of the surface of sample 1.The shape of press strip 6 shown in Fig. 2 is the glide direction length of width 10mm, sample The lower part of 5mm, glide direction both ends are made of the curved surface of curvature 1mmR, the press strip lower surface of extruded sample have width 10mm, The plane of glide direction length 3mm.The shape of press strip 6 shown in Fig. 3 is the glide direction length 59mm of width 10mm, sample, The lower part at glide direction both ends is made of the curved surface of curvature 4.5mmR, and extruded sample press strip lower surface has width 10mm, sliding The plane of direction length 50mm.
Measuring friction coefficient test is carried out under the conditions of as shown below 2.
[condition 1]
Using press strip shown in Fig. 2, presses load N and be set as 400kgf, (the horizontal of sliding stand 3 moves the hauling speed of sample Dynamic speed) it is set as 100cm/min.
[condition 2]
Using press strip shown in Fig. 3, presses load N and be set as 400kgf, (the horizontal of sliding stand 3 moves the hauling speed of sample Dynamic speed) it is set as 20cm/min.
Friction coefficient μ between material to be tested and press strip is with formula: μ=F/N is calculated.
(ii) confficient of static friction measurement test: imaginary extension (stretch-formed part)
Compression moulding simulation is carried out, result is clear, and in surface pressing be 7MPa or less and sliding speed is 50mm/ Forming part etc. (is stretched out) in the position below min, compared with dynamic friction coefficient, confficient of static friction and actual compression moulding Correlation is higher.Therefore, it in order to evaluate compression moulding (the especially mouldability of extension), measures in the following manner each for examination The confficient of static friction of material.Fig. 4 is the brief diagram for indicating the confficient of static friction measurement device using experimental rig 10.Such as the figure institute Show, by the confficient of static friction measurement sample 100 taken from material to be tested with constant load P=370kgf by compression mould 11,12 Afterwards, the sample 100 clamped with the speed drawing of 10mm/min by mold 11,12.It is constant with the measuring space of 0.005Hz as a result, Load F ' needed for the traction of load P and sample 100.Confficient of static friction μ is with formula: μ=F '/P is calculated, after acquirement sliding starts Peak value coefficient of friction as confficient of static friction.It should be noted that the shape of mold 11 is the glide direction of width 35mm, sample The lower part of length 14mm, glide direction both ends are made of the curved surface of curvature 2mmR, and the press strip lower surface for pressing sample has width The plane of 35mm, glide direction length 10mm.The shape of mold 12 is the glide direction length 24mm of width 35mm, sample, sliding The lower part at dynamic direction both ends is made of the curved surface of curvature 2mmR, and the press strip lower surface for pressing sample has width 35mm, sliding side To the plane (the following conditions 3) of length 20mm.It should be noted that squeezing SUGIMURA Chemical Industrial corporation Pressure uses cleaning oil PRETON (registered trademark) R352L to be tested as the surface that lubricating oil is coated on sample 100.
(3) evaluation method of degreasing
The evaluation of degreasing is carried out with the water wettability power after degreasing.By Industrial plants of formulas of SUGIMURA Chemical The extruding of commercial firm is coated on single side 2.0g/m to manufactured test film with cleaning oil PRETONR352L2Afterwards, using Japanese pa card The alkaline degreaser of the FC-L4460 of rapids essence Co. Ltd. system (NIHON PARKERIZING CO., LTD.) carries out the de- of sample Rouge.Extruding by adding the SUGIMURA Chemical Industrial Co. Ltd. system of 10g/L in advance to degreaser is used Oil PRETONR352L is cleaned, the deterioration in the alkaline degreaser of auto production line is simulated.Here, degreasing time is set as 60 seconds, temperature Degree is set as 37 DEG C.When degreasing, the propeller of diameter 10cm is stirred into degreaser with the speed of 150rpm.Measurement terminates 20 from degreasing Thus the water wettability power of test film after second carries out the evaluation of degreasing.
(4) evaluation of appearance unevenness
Evaluation appearance is uneven by visual observation.On the basis of appearance sample shown in fig. 5,1~5 point of scoring and progress are provided Evaluation.It should be noted that 4 points indicated above good, 5 points of expressions are better.
Table 2 (merging table 2-1 and table 2-2 as table 2) will be shown in by result from above.
The following item known to table 1,2.
The compression moulding for not carrying out the comparative example of the No.1 of oxide skin(coating) formation processing and neutralisation treatment is poor.No.2 be into Oxide skin(coating) of having gone forms processing and neutralisation treatment, but the comparison of P ion, carbanion is not added in alkaline aqueous solution Example.The compression moulding of a part, appearance are good, but the compression moulding of a part without sufficient P, C in the oxide layer Property, degreasing are poor.
No.3~7 are to have carried out oxide skin(coating) to form processing and neutralisation treatment, but be not added with carbonic acid in alkaline aqueous solution The comparative example of radical ion.In oxide skin(coating) without sufficient C and degreasing is insufficient, have appearance uneven.Due to oxide skin(coating) It dissolves and compression moulding decline.
No.30 is the comparative example for not adding P ion fully in alkaline aqueous solution.Sufficient P is free of in oxide skin(coating) And degreasing is poor.
No.37 is the comparative example for not adding carbanion fully in alkaline aqueous solution.It is free of in the oxide layer Sufficient C, due to oxide skin(coating) dissolution and compression moulding is insufficient, degreasing is poor.There is appearance uneven.
Not there is no sulfate ion in the formation treatment fluid of oxide skin(coating) in No.50,51, be insufficient from this respect Example (comparative example).The compression moulding of a part is good, but the compression moulding of a part without S, C in the oxide layer Property, degreasing, appearance unevenness are also insufficient.
No.65~67 sufficiently exist in neutralisation treatment liquid outside the range that P ion, carbanion but pH are pH9~12, It is insufficient example (comparative example) from this respect.The compression moulding of a part is good, but is free of in the oxide layer Sufficient C and the compression moulding of a part, degreasing, appearance are insufficient.
No.68 is to form the comparative example for not implementing to wash between processing and neutralisation treatment in oxide.The compacting of a part Good forming ability, but in the oxide layer without sufficient P, C and the compression moulding of a part, degreasing, appearance are insufficient.
No.8~29,31~36,38~49,52~64 are to carry out oxide skin(coating) to form processing and neutralisation treatment, condition It also is the example of preferred scope.It include sufficient Zn, S, P, C in oxide skin(coating), compression moulding and degreasing are excellent, appearance Also good.
No.38 is carried out detailed by film analysis.
CO can be confirmed between 150 DEG C~500 DEG C known to the result of gaschromatographic mass spectrometric analysis2Releasing, C is with carbonate Form exist.
Analyzed using x-ray photoelectron spectroscopy, as a result known to observed near 987eV and be equivalent to Zn LMM's Peak, Zn exist with the state of zinc hydroxide.Similarly, the peak for being equivalent to S 2p is observed near 171eV, S is with sulfate Form exists.
It is analyzed using X-ray absorption fine structure spectrometer, as a result knows to observe near 2153,2158,2170eV To peak, P exists in the form of pyrophosphate.
It observes that 11.2% weight is reduced at 100 DEG C or less known to the result of differential thermal balance, contains the crystallization water.
X-ray diffraction as a result, 2 θ be 8.5 °, 15.0 °, 17.4 °, 21.3 °, 23.2 °, 26.3 °, 27.7 °, 28.7 °, 32.8 °, 34.1 °, 58.6 °, 59.4 ° are nearby observed diffraction maximum.
Contain Zn known to result above and composition ratio, charge balance4(SO4)0.95(CO3)0.05(OH)6·3.3H2O table The crystal structure substance shown.
No.39 is carried out detailed by film analysis.
CO can be confirmed between 150 DEG C~500 DEG C known to the result of gaschromatographic mass spectrometric analysis2Releasing, C is with carbonate Form exist.
Analyzed using x-ray photoelectron spectroscopy, as a result known to observed near 987eV and be equivalent to Zn LMM's Peak, Zn exist with the state of zinc hydroxide.It will also be appreciated that observing the peak for being equivalent to S 2p near 171eV, S is with sulfate Form exists.
It is analyzed using X-ray absorption fine structure spectrometer, as a result knows to observe near 2153,2158,2170eV To peak, P exists in the form of pyrophosphate.
It observes that 9.4% weight is reduced at 100 DEG C or less known to the result of differential thermal balance, contains the crystallization water.
X-ray diffraction as a result, 2 θ be 8.8 °, 15.0 °, 17.9 °, 21.3 °, 23.2 °, 27.0 °, 29.2 °, 32.9 °, 34.7 °, 58.9 ° are nearby observed diffraction maximum.
Containing by Zn known to result above and composition ratio, charge balance4(SO4)0.8(CO3)0.2(OH)6·2.7H2O table The crystal structure substance shown.
No.40 is carried out detailed by film analysis.
CO can be confirmed between 150 DEG C~500 DEG C known to the result of gaschromatographic mass spectrometric analysis2Releasing, C is with carbonate Form exist.
Analyzed using x-ray photoelectron spectroscopy, as a result known to observed near 987eV and be equivalent to Zn LMM's Peak, Zn exist with the state of zinc hydroxide.
It will also be appreciated that observing the peak for being equivalent to S 2p near 171eV, S exists in the form of sulfate.
It is analyzed using X-ray absorption fine structure spectrometer, as a result knows to observe near 2153,2158,2170eV To peak, P exists in the form of pyrophosphate.
It observes that 35.5% weight is reduced at 100 DEG C or less known to the result of differential thermal balance, contains the crystallization water.
X-ray diffraction as a result, 2 θ be 8.9 °, 15.0 °, 18.3 °, 21.3 °, 23.2 °, 27.4 °, 29.5 °, 32.9 °, 34.7 °, 58.9 ° are nearby observed diffraction maximum.
By result above and composition ratio, charge balance it is found that containing Zn4(SO4)0.75(CO3)0.25(OH)6·10.0H2O The crystal structure substance of expression.
No.41 is carried out detailed by film analysis.
CO can be confirmed between 150 DEG C~500 DEG C known to the result of gaschromatographic mass spectrometric analysis2Releasing, C is with carbonate Form exist.
Analyzed using x-ray photoelectron spectroscopy, as a result known to observed near 987eV and be equivalent to Zn LMM's Peak, Zn exist with the state of zinc hydroxide.
It will also be appreciated that observing the peak for being equivalent to S 2p near 171eV, S exists in the form of sulfate.
It is analyzed using X-ray absorption fine structure spectrometer, as a result knows to observe near 2153,2158,2170eV To peak, P exists in the form of pyrophosphate.
It does not observe that big weight is reduced at 100 DEG C or less known to the result of differential thermal balance, does not contain the crystallization water.
X-ray diffraction as a result, 2 θ be 8.9 °, 15.0 °, 18.3 °, 21.3 °, 23.2 °, 27.4 °, 29.5 °, 32.9 °, 34.7 °, 58.9 ° are nearby observed diffraction maximum.
By result above and composition ratio, charge balance it is found that containing Zn4(SO4)0.7(CO3)0.3(OH)6The crystal of expression Structural material.
No.42 is carried out detailed by film analysis.
CO can be confirmed between 150 DEG C~500 DEG C known to the result of gaschromatographic mass spectrometric analysis2Releasing, C is with carbonate Form exists.
It is analyzed using x-ray photoelectron spectroscopy, is as a result equivalent to Zn LMM it is found that observing near 987eV Peak, Zn exists with the state of zinc hydroxide.
It will also be appreciated that observing the peak for being equivalent to S 2p near 171eV, S exists in the form of sulfate.
It is analyzed using X-ray absorption fine structure spectrometer, as a result knows to observe near 2153,2158,2170eV To peak, P is with the presence of pyrophosphate.
It observes that 18.6% weight is reduced at 100 DEG C or less known to the result of differential thermal balance, contains the crystallization water.
X-ray diffraction as a result, 2 θ be 9.1 °, 15.0 °, 18.4 °, 21.3 °, 23.2 °, 27.7 °, 29.7 °, 32.9 °, 34.7 °, 58.9 ° are nearby observed diffraction maximum.
By result above and composition ratio, charge balance it is found that containing Zn4(SO4)0.6(CO3)0.4(OH)6·5.0H2O table The crystal structure substance shown.
For other embodiments, zinc hydroxide, sulfate, carbonate, pyrophosphate, crystallization are also confirmed with identical step The presence of water, and to whether containing Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure object that O is indicated is investigated.Confirmation To exist and containing the case where be set as zero, be not confirmed the case where be set as ×, the result of investigation is shown in table 2 (for whether there is or not knots Brilliant water is not shown in table).Know example of the present invention and No38~40,42 similarly, the presence of zinc hydroxide, sulfate, carbonate, coke Phosphate, the crystallization water, contain Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure object that O is indicated.
Embodiment 2
Galvanizing by dipping processing is implemented to the cold-rolled steel sheet of plate thickness 0.7mm, then, carries out skin-pass.Next, for one Part carries out the surface activation process using alkaline aqueous solution using the alkaline aqueous solution for the condition shown in table 3 that is adjusted to.It connects , it is handled as oxide skin(coating) formation, steel plate is impregnated in the sulfuric acid solution for being adjusted to condition shown in table 3, squeezed with roller After pressure, kept for the stipulated time shown in table 3.Then, dry after being washed.Next, under the conditions shown in Table 3 into Row neutralisation treatment.Sulfate ion concentration in sulfuric acid solution is 15g/L.
Thickness to the oxide skin(coating) for measuring surface by hot-dip galvanized steel sheet obtained above, and utilization and embodiment Identical step evaluation compression moulding (sliding properties) and degreasing, appearance unevenness.
Table 4 will be shown in by result from above.
The following item known to table 3,4.
The compression moulding for not carrying out the comparative example of the No.69 of oxide skin(coating) formation processing and neutralisation treatment is poor.
No.70 is to have carried out oxide skin(coating) to form processing and neutralisation treatment but be not added with carbonate in alkaline aqueous solution The comparative example of ion and P ion.Sufficient P, C are free of in oxide skin(coating), compression moulding, appearance are good, but degreasing is poor.
No.71~75 are to have carried out oxide skin(coating) to form processing and neutralisation treatment but be not added with carbon in alkaline aqueous solution The comparative example of acid ion.Sufficient C is free of in the oxide layer, and degreasing is insufficient, poor appearance.It is molten due to oxide skin(coating) It solves and compression moulding decline.
No.76~80 are to have carried out oxide skin(coating) to form the invention that processing and neutralisation treatment, its condition are also preferred scope Example.Contain sufficient Zn, S, P, C in the oxide layer, compression moulding and degreasing are excellent, and appearance is also good.
No.81~90 be carried out activation processing, oxide skin(coating) formation processing, neutralisation treatment, its condition are also preferred model The example enclosed.Contain sufficient Zn, S, P, C in the oxide layer, compression moulding and degreasing are excellent, and appearance is also good. Know that compression moulding is more excellent especially compared with No.76~79.
For the whole embodiments of embodiment 2, zinc hydroxide, sulfate, carbonic acid are confirmed with step same as Example 1 The presence of salt, pyrophosphate, the crystallization water, and to whether containing Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure that O is indicated Object is investigated.Confirm in the presence of and containing the case where be set as zero, be not confirmed the case where be set as ×, the result of investigation is shown in It (for there is no crystal water, is not shown in table) in table 4.Known to example of the present invention and No38~40,42 similarly, the presence of zinc hydroxide, Sulfate, carbonate, pyrophosphate, the crystallization water, contain Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure object that O is indicated.
Embodiment 3
Electrogalvanizing processing is implemented to the cold-rolled steel sheet of plate thickness 0.7mm.Next, using condition shown in table 5 is adjusted to Alkaline aqueous solution carries out the surface activation process using alkaline aqueous solution.Then, it is handled as oxide skin(coating) formation, steel plate is soaked Stain is in the sulfuric acid solution for being adjusted to condition shown in table 5, after squeezing with roller, is kept for the stipulated time shown in table 5.Then, It is dry after being washed.Next, being neutralized under the conditions shown in Table 5.Sulfate radical in sulfuric acid solution Ion concentration is 15g/L.
To by plated steel sheet obtained above measure surface oxide skin(coating) thickness, and by with embodiment 1 Identical step evaluation compression moulding (sliding properties) and degreasing.Table 6 will be shown in by result from above.
The following item known to table 5,6.
The compression moulding for not carrying out the comparative example of the No.91 of oxide skin(coating) formation processing and neutralisation treatment is poor.
No.92 is to have carried out oxide skin(coating) to form processing and neutralisation treatment but be not added with carbonate in alkaline aqueous solution The comparative example of ion and P ion.Sufficient P, C are free of in the oxide layer, and compression moulding, appearance are good, but degreasing is poor.
No.93~97 are to have carried out oxide skin(coating) to form processing and neutralisation treatment but be not added with carbon in alkaline aqueous solution The comparative example of acid ion.Sufficient C is free of in the oxide layer, and degreasing is insufficient, has appearance uneven.Due to oxide skin(coating) Dissolution and compression moulding decline.
No.98~102 are to have carried out oxide skin(coating) to form the invention that processing and neutralisation treatment, its condition are also preferred scope Example.Contain sufficient Zn, S, P, C in the oxide layer, compression moulding and degreasing are excellent, and appearance is also good.
No.103~112 be carried out activation processing, oxide skin(coating) formation processing, neutralisation treatment, its condition are also preferred The example of range.Contain sufficient Zn, S, P, C in the oxide layer, compression moulding and degreasing are excellent, and appearance is also good It is good.Know that compression moulding is more excellent especially compared with No.98~102.
For the whole embodiments of embodiment 3, zinc hydroxide, sulfate, carbonic acid are confirmed with step same as Example 1 The presence of salt, pyrophosphate, the crystallization water, and to whether containing Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure that O is indicated Object is investigated.Confirm in the presence of and containing the case where be set as zero, be not confirmed the case where be set as ×, the result of investigation is shown in It (for there is no crystal water, is not shown in table) in table 6.Known to example of the present invention and No38~40,42 similarly, the presence of zinc hydroxide, Sulfate, carbonate, pyrophosphate, the crystallization water, contain Zn4(SO4)1-X(CO3)X(OH)6·nH2The crystal structure object that O is indicated.
Symbol description
1 measuring friction coefficient sample
2 sample tables
3 sliding stands
4 rollers
5 sliding stand supporting tables
6 press strips
7 the 1st load cells
8 the 2nd load cells
9 guide rails
N presses load
F resistance to sliding
10 confficient of static friction measurement devices
11 molds
12 molds
100 measuring friction coefficient samples
P presses load
F ' traction load

Claims (24)

1. a kind of zinc-based metal plated steel sheet, which is characterized in that the zinc-plated system layer for having steel plate and being formed on the steel plate,
Zinc-plated system's layer has the oxide skin(coating) of average thickness 20nm or more on surface layer,
The oxide skin(coating) is made of Zn, O, H, S, C, P and inevitable impurity, contains 50mg/m2Above Zn, the 5mg/m2 Above S, the 0.2mg/m2Above C, the 0.2mg/m2Above P,
In the oxide skin(coating), there are sulfate, carbonyldioxy, hydroxyl and phosphates.
2. zinc-based metal plated steel sheet as described in claim 1, which is characterized in that include Zn in the oxide skin(coating)4(SO4)1-X(CO3)X (OH)6·nH2The crystal structure object that O is indicated, here, X are the real number of 0 < X < 1, and n is the real number of 0≤n≤10.
3. zinc-based metal plated steel sheet as claimed in claim 1 or 2, which is characterized in that
Containing selected from PO in the oxide skin(coating)4 3-、P2O7 4-、P3O10 5-Inorganic acid or one or more of metallic compound,
The metallic compound contains selected from one or more of sodium and zinc.
4. zinc-based metal plated steel sheet as claimed in claim 1 or 2, which is characterized in that zinc-based metal plated steel sheet is alloyed hot-dip zinc-coated steel Plate, hot-dip galvanized steel sheet or plated steel sheet.
5. zinc-based metal plated steel sheet as claimed in claim 3, which is characterized in that zinc-based metal plated steel sheet be alloyed hot-dip galvanized steel plate, Hot-dip galvanized steel sheet or plated steel sheet.
6. a kind of manufacturing method of zinc-based metal plated steel sheet is the manufacturer of zinc-based metal plated steel sheet according to any one of claims 1 to 5 Method, which is characterized in that have following process:
Oxide skin(coating) formation process is kept for 1~60 second after contacting zinc-based metal plated steel sheet with the acid solution containing sulfate ion, It followed by washes, wherein the sulfate ion concentration in the acid solution is 0.5g/L or more, the pH of the acid solution It is 0.5~5.0；And
The surface of neutralisation treatment operation, the oxide skin(coating) formed in making the oxide skin(coating) formation process connects with alkaline aqueous solution It is kept in the state of touching 0.5 second or more, followed by washes, is dry；
The alkaline aqueous solution, which contains, to be calculated as the P ion of 0.01g/L or more with P concentration, is calculated as 0.1g/ with carbon acid ion concentration The carbanion of L or more, pH are 9~12.
7. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 6, which is characterized in that the alkaline aqueous solution, which contains, to be selected from The phosphorus compound and carbonate of one or more of phosphate, pyrophosphate and triphosphate.
8. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that containing dense with carbanion Degree is calculated as the carbanion of 0.6g/L or more.
9. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that containing dense with carbanion Degree is calculated as the carbanion of 1.2g/L or more.
10. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that containing with carbon acid ion concentration It is calculated as the carbanion of 1.2g/L or more.
11. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that the pH of the alkaline aqueous solution It is 9~12, temperature is 20~70 DEG C.
12. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that the pH of the alkaline aqueous solution is 9 ~12, temperature is 20~70 DEG C.
13. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that the acid solution has pH Buffer function, range of the pH rising degree 0.003~0.5, the pH rising degree be pH by making the acid solution of 1L from 2.0 rise to 5.0 needed for the amount L of 1.0mol/L sodium hydroxide solution define.
14. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that the acid solution is slow with pH Punching effect, range of the pH rising degree 0.003~0.5, the pH rising degree are pH by making the acid solution of 1L from 2.0 What the amount L of 1.0mol/L sodium hydroxide solution needed for rising to 5.0 was defined.
15. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that the acid solution contains conjunction That counts 5~50g/L is selected from acetate, phthalate, citrate, succinate, lactate, tartrate, borate With the salt of one or more of phosphate, pH is 0.5~5.0, and liquid temperature is 20~70 DEG C.
16. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that the acid solution contains total 5 ~50g/L's is selected from acetate, phthalate, citrate, succinate, lactate, tartrate, borate and phosphorus The salt of one or more of hydrochlorate, pH are 0.5~5.0, and liquid temperature is 20~70 DEG C.
17. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that the oxide skin(coating) forms work In sequence, the acid solution adhesion amount of the surface of steel plate after the acid solution contact is 15g/m2Below.
18. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that the oxide skin(coating) formation process In, the acid solution adhesion amount of the surface of steel plate after the acid solution contact is 15g/m2Below.
19. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that the zinc-based metal plated steel sheet is to close Aurification hot-dip galvanized steel sheet, hot-dip galvanized steel sheet or plated steel sheet.
20. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that the zinc-based metal plated steel sheet is alloy Change hot-dip galvanized steel sheet, hot-dip galvanized steel sheet or plated steel sheet.
21. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that implementing zinc-plated system to steel plate Afterwards, before the oxide skin(coating) formation process, by making steel plate and the aqueous solution of alkalinity make surface active and contact.
22. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that after implementing zinc-plated system to steel plate, Before the oxide skin(coating) formation process, by making steel plate and the aqueous solution of alkalinity make surface active and contact.
23. the manufacturing method of zinc-based metal plated steel sheet as claimed in claims 6 or 7, which is characterized in that implementing zinc-plated system to steel plate Afterwards, before the oxide skin(coating) formation process, implement skin-pass.
24. the manufacturing method of zinc-based metal plated steel sheet as claimed in claim 8, which is characterized in that after implementing zinc-plated system to steel plate, Before the oxide skin(coating) formation process, implement skin-pass.
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